Method of treating petroleum



Mar h 29 1927.

? R. CROSS METHOD OF TREATING PETROLEUM Filed April 26. 1924 Twea 22 729' 70 we,

Patented Mar. 29, 19 27.

UNED STATES ROY CROSS, OF KANSAS CITY, MISSOURI.

METHOD OF TREATING PETROLEUM.

Application filed April 26,

This invention relates to a process of treating fluid petroleum hydrocarbons for removal of sulphur, color and disagreeable odors. It more particularly relates to treatment with molecular chlorine.

Among the various sulphur bearing compounds found in petroleum or produced by the action of chlorine are the following (R being the alkyl radical) Mercaptans, thio-alcohols or alkyl hydrosulphideszRHs.

Alkyl sulphides or thio-etherszR s.

Alkyl disulphideszR S.

Sulphine or sulphonium compounds: R 801.

Sulphones=R SO Sulphonic acids RI-ISO...

Thio-sulphonic acids:RHS O Sulphinic acids=RHSO Sulph0-chl0rides=RClSO Chlorine in active condition in the form of hypochlorite has commonly been used for the treatment of oil but molecular chlorine has not been so used. Hypochlorite has ordinarily been applied in aqueous solutions.

Among the reactions of chlorine on various hydrocarbons and sulphur compounds in petroleum are the following:

Most of the above compounds are soluble in hydrocarbons or petroleum and very few are soluble in water. However, the compound R SCl is soluble in water. One of the purposes of this invention therefore, is to so treat the sulphur compounds of petroleum, that an alkyl halide RC1 is formed. Such a reaction may be carried out by first dissolving chlorine gas in cold petroleum. The solution is usually efi'ected to the extent of about one pound per gallon. -This physical dissolving of the chlorine may preferably be carried out in the dark so as to prevent an excessive chemical action. After the physical solution is complete, the proper amount of light preferably from a source of ultra violet light, may be applied inducing the reaction:

Numerous other side reactions of course, the nature of which is-not known, are roduced. It is desirable first to produce an a lhalide 1924. Serial No. 709,269.

as shown above or a reaction similar to the However, this last reaction is of comparative unimportance as it is desired first to treat a relatively small stream of the oil, which small stream is then applied with the main. flow. A typical condition would be the use of one pound of chlorine to one gallon of benzine or petroleum; This one gallon would ordinarily be suflicient to treat at least two barrels of oil. Obviously, the amount to treat would depend upon the amount of sulphur in the petroleum and its solvent properties for chlorine as well as the condition in which the sulphur exists in the petroleum. When the smaller heavily treated portion of the petroleum is mixed with the larger portion of the petroleum,

secondary reactions take place of which the following is an example:

The products R SCl are fairly soluble in water and can be washed out of the petroleum by thorough agitation with water. A'

large portion of the by-product sulphur compounds produced simultaneously are now readily reacted upon with sodium plumbite or doctor solution. l/Vhile the above method of treatment is not necessary to get fairly good results it is desirable, as chlorine may be added direct to the main body of the stream of oil to be treated. A typical operation would be applied to ordinary pressure distillate in which in a continuous agitator with a constantly flowing stream of benzine, a comparatively small stream of this benzine would be diverted to a tile absorption, tower. The chlorine gas would be introduced at the bottom of this tile absorption tower and the petroleum at the top, the tower being filled with a large amount of broken tile or similar material with or without catalytic agents mentioned below, to present a large absorbing surface. This minor stream of oil would then be mixed with the major flow for the treatment of the major body of oil. In a typical instance in the treatment of 1,000 barrels of oil, the minor flow represents ten barr ils of oil and the major flow, 990 barrels o 01 The single figure depicts an apparatus in which this process may be carried on. At 1 is shown an absorption .tower containing broken inert material such as ceramic substances. At 2 is a continuous agitator; 3 is a line from any suitable source of supply through which pressure distillate is introduced to the system. The line 3 terminates in a T connection to which is connected a line 4 through which a minor flow of the pressure distillate is directed into the top of the absorption tower. To the o posite connection is a line 5 by means 0 which the major flow of pressure distillate is directed to the top ofthe continuous agitator. The chlorine is introduced to the bottom of the agitator through the line 6 and rises in an opposed direction to the gravitating distillate comin in intimate contact with the distillate in its travel through the absorption tower packing. The unabsorbed chorine is drawn ofi from the top of the tower through the line 7. Eight (8), 9, 10 and 11 are valves controlling the respective lines in which they are placed. Twelve (12) is a draw off line from the continuous agitator for removing the treated major flow of the pressure distillate. Thirteen (13) is a valve controlling this line. Fourteen (14) is a line communicating between the bottom of the absorption tower 1 and the line 5 through which the major flow of untreated pressure distillate is introduced into the top of the continuous agitator. The minor flow of treated pressure distillate is introduced to the major flow of the distillate near the top of the continuous agitator prior to the introduction of the major flow of distillate into the tower. Aftor combination, the distillate is subjected to a thorough mixture in the agitator at which time the treated minor flow is completely incorporated and the major flow of distillate effecting complete treatment of the pressure distillate stream. Avalve 15 is interposed in the line 14 for regulating the amount of minor flow of treated distillate introduced to the major flow.

The application of ultra violet rays of light or catalytic agents is made preferably to the minor flow but may be to the major flow. In addition to or instead of the catalytic action of light, chlorination may be effected in the presence of iron or iron chloride. aluminum 01' aluminum chloride, molybdenum chloride, nickel chloride, mangaof water.

paratus such as is used for the sterilization After this treatment, the oil is thoroughly washed with water, this being followed by the so-called doctor solution, sodium plumbite or other well known methods of treatment. It may also be finally treated with clay or acid treated clay or acid and copper treated clay.

I claim:

1. The method of treating petroleum products which comprises creating major and minor flow streams of oil adding to a minor flow of oil, molecular chlorine submitting such minor flow to the action of light and combining the minor flow of the product with a major flow.

2. The method of treating petroleum products which consists in creating major and minor flow streams of oil adding to a minor flow of oil, molecular chlorine and combining the treated minor flow with a major flow of oil.

3. The method of treating petroleum products which consists in establishing major and minor flow streams of oil to be treated dissolving chlorine in a minorflow of oil in the absence of light and in the presence of a chemical catalyst, submitting this minor flow to the action of light then combining the minor flow with the major flow and then subjecting a major flow of oil to the action of light having a catalytic effect.

4. The method of treating petroleum products which consists in establishing major and minor flow streams of oil to be treated dissolving chlorine in the minor flow of such product in the absence of light submitting this minor flow to the action of. light then returning the minor flow to the'major flow and then subjecting the major flow to the action of light and washing the major flow with water and sodium plumbite solution.

5. A method of treating mineral oil, consisting in adding molecular chlorine to a reatively small volume thereof, and allowing this mixture to react in the presence of a catalyst, then combining, for secondary reaction, this mixture with a relativelylarger volume of oil.

ROY CROSS. 

